Certain water-soluble high molal oxyalkylated esters



tially matured as U. S. Patent Patented Nov 21, 1944 CERTAINWATER-SOLUBLE HIGH MOI-AL OXYALKYLATED ESTERS Melvin De Groote,University City, and Bern-. hard Keiser, Webster Groves, Mo., assignorsto Petrolite Corporation, Ltd., Wilmington, Del., a corporation ofDelaware No Drawing.

Original application March 21,

1941, Serial No. 384,599. Divided and this appiication June 26, 1942,Serial No. 448,685

6 Claims.

This invention relates to a new chemical product or compound, ourpresentapplication being a division of our co-pending application Serial No.384,599, filed March 21, 1941, which substan- September 8 1942.

One object of our present invention is to provide a new material,compound or composition of matter, that is capable of use forvarious'purposes, and particularly. adapted for use as a demulsifier inthe resolution of crude oil emulsions. Another object of our inventionis to provide a practicable method for manufacturing said new material,compound or composition of matter.

The new chemical compound or composition of matter which constitutes ourpresent invention is exemplified by the acid, or preferably, neutralester derived by complete esterification of one mole ofa polyalkyleneglycol of the kind hereinafter described, with two moles of a fractionalester derived from a hydroxylated material of the kind herein described,and a polybasic carboxy acid having not over six carbon atoms- No.2,295,167, dated I If a hydroxylated material, indicated for the sake ofconvenience, by the formula T.0I-I, is reacted with a polybasic carboxyacid, which, similarly, may conveniently be indicated as being of thedibasic type, by the formula HOOC.D.COOH, then the fractional esterobtained by reaction between equimolar quantities may be indicated bythe following formula:

HOOC.D.COO.T

in which m varies from 7 through 17.

Instead of polyethylene glycols, one may use polypropylene glycols orpolybutylene glycols. Thus, for convenience, in the broadest aspect, the

. polyalkylene glycols employed may be indicated by the followingformula:

OH(CnH2nO) mH in which m has its previous significance and n representsa numeral varying from 2 to 4.

Thus, the bulk of the materials herein contemplated, particularly foruse as .demulsifiers, may be indicated within certain variations, as

- hereinafter stated, by the neutral ester derived product.

by esteriflcation of one mole of a glycol ofthe kind above described,with two moles of a fractional ester of the kind previously indicated.The formation of the com ound may be indicated bythe following reaction,although obviously it is immaterial what particular procedure isemployed to produce the particular chemical compound or product:

As indicated previously, the polybasic acids employed are limited to thetype having not more than six carbon atoms, for example, oxalic,malonic, succinic, glutaric, and adipic. Similarly,

one may employ acids such as fumaric, maleic, glutaconic, and variousothers, including citric,

manufacture of the finished ester, and also of the price of thereactants. Generally speaking, the higher the temperature employed,easier it is to obtain large yields of the esterlfied Although oxalicacid is comparatively cheap, it decomposes somewhat readily at slightlyabove the boiling point of water. For this reason, it is more desirableto use an acid which is more resistant to pyrolysis. Similarly, when apolybasic acid is available in the form of an anhydride, such anhydrideis apt to produce the ester with greater case than the acid itself. Forthis reason, maleic anhydride is particularly adaptable; and also,everything else considered, the cost is comparatively low on a per molarbasis, even though somewhat higher on a per pound basis. Succinic acidor the anhydride has many of the attractive qualities of maleicanhydride; and this is also trueof adipic acid. For purposes of brevity,the bulk of the compounds hereinafter illustrated will refer to the useof maleic anhydride, although it is understood that any other suitablepolybasic acid may be employed. Furthermore, for purposes ofconvenience, reference is made to the use of polyethylene glycols. Ashas been previously indicated, such glycols can be replaced by suitablepolypropylene or polybutylene compounds.

As far as the range oi oxyalkylated compounds employed as reactants isconcerned, it is our preference to employ those having approximately8-12 oxyalkylene groups, particularly 8-12 onethylene groups. Thepreference to use the oxyethylated compounds is due, largely, to thefact that they are commercially available, and particularly so in twodesirable forms. The most desirable form is the so-called nonaethyleneglycol, which, although consisting largely of nonaethylene glycol, maycontain small amounts of heptaethylene and octaethylene glycols, andpossibly minor percentages of the higher homologs. Such glycolsrepresent the upper range of distillable glycols; and they may beconveniently re-. ferred to as upper distillable ethylene glycols. Thereis no particularly good procedure for making a sharper separation on acommercial scale; and it is understood that mixtures of one or more ofthe glycols may be employed, as well as a. single glycol. As pointedout, it is particularly preferred to employ nonaethylene glycol ascommercially available, although it is understood that this productcontains other' homologs as indicated.

Substantially as desirable as the upper distillable polyethyleneglycols, are the lower nondistillable polyethylene glycols. Thesematerials are available, in the form of a waxy water-soluble material,and the general range may vary somewhat from decato tetradeca-ethyleneglycol. As is well understood, the method of producing such glycolswould cause some higher homologs to be formed; and thus, even in thisinstance there may be present some oxyethylene glycols within the higherrange above indicated. One need not point out that these particularcompounds consist of mixtures, and that in some instances, particularlydesirable esters are obtained by making mixtures of the liquidnonaethylene glycol with the soft, waxy. lower non-distillablepolyethylene glycols. For the sake of convenience, reference in theexamples will be to nonaethylene glycol; and calculations will be basedon a theoretical molecular weight of 414. Actually, in manufacture, themolecular weight of the glycol employed, whether a higher distillablepolyethylene glycol, or a lower non-distillable polywhich replaces thesulfonic acid hydrogen atom, may be indicated by the following formula:

It will be pointed out subsequently that quite a variety of hydroxylatedesters of high mole sulfonic acids are obtainable which correspond tothe above generic formula. In many instances T, instead of representinga hydrocarbon radical,

will represent a hydrophobe radical, in which the to high molalalcohols. A material of the kind ethylene glycol, or a mixture of thesame, should I be determined and reaction conducted on the basis of suchdetermination, particularly in conjunction with thehvdroxy or acetylvalue.

It has been previously pointed out that it is immaterial how thecompounds herein contemplated are manufactured, although we have foundit most desirable to react the selected glycol or mixtures of glycolswith maleic anhydride in a ratio of two moles of the anhydride for onemole of the glycol. Under such circumstances, we have found littletendency to form longer chain polymers; and in fact, the product ofreaction, if conducted at reasonably low temperatures, appears to belargely monomeric. For convenience, such intermediate product may thenbe considered as a dibasic or polybasic acid. One mole of theintermediate so obtained is then reacted with two moles of the alcoholicmaterial of the kind subsequently described.

It is to be noted, however, that if one prepares a fractional acidicester, then if two moles of the fractional acidic ester are reacted withone mole of the polyethylene glycol, there is no possibility for theformation of polymeric types of esterification products under ordinaryconditions. If a high molal sulfonic acid be indicated by theconventional formula R.SOaH

then a hydroxylated ester which may actually have more than one hydroxylgroup in the radical 7 above described illustrates the compounds here incontemplation with certain added provisos:

(a) That the sulfonic acid in the form of a salt or acid, besurface-active, as subsequently defined; and- (b) That the ester derivedtherefrom and containing the hydroxy alkyl group or its equivalent, bewater-insoluble.

As has been indicated, the compounds herein contemplated are derivativesof surface-active sulfonic acids, which, generally speaking, are

water-soluble, but in some instances, such as in the case of petroleummahoganyacids, may be essentially oil-soluble, although such oil-solubleacids may also show water-solubility to a greater or lesser degree,particularly in the form of sodium, potassium, or ammonium salts. Suchsulcomparison with distilled water, Where the sulfonic acids or theirsalts are oil-soluble, surfaceactivity may be indicated by the abilityor characteristic property of producing water-in-oil emulsons, andsometimes by the ability to cause oily vehicles to foam or froth.Usually, the acids themselves show the same surface-active property asthe salts.

Although the types of compounds herein described, and the method we havedevised for producing said compounds are also new, certain of the rawmaterials used in the manufacture of said chemical compounds, forexample, certain surface-active sulfonic acids, are well knowncompositions of matter. In order to show the wide range of suitablesulfonic acids, brief reference will be made to a variety of suchmaterials.

More specifically, in the manufacture of compounds of the kind hereincontemplated, one may employ as raw materials petroleum sulfonic acids,fatty sulfonic acids, fatty aromatic sulfonic acids, alkylatedmonocarbocyclic sulfonic acids, alkylated non-hydrogenated dicarbocyclicsulfonic acids, partially or completely hydrogenated alkylateddicarbocyclic sulfonic acids, alkylated polycarbocyclic sulfonic acidscontaining at least three nuclei, cycloalkylated carbocyclic sulfonicacids generally be obtained by some conventional pro or dispersible.

2,sas,o4e 3 See U. s. Patent No. 628,503, dated July 11, 1899,

eedure, as, for example, dissolving the sodium sulionic acid salt in anysuitable low molal alcohol, passing in hydrochloric acid gas with theprecipitation of sodium chloride, and the liberation of a sulfonic acidwhich is usually soluble in the alcoholic medium. The alcoholicsolutionof the sulionic acid can be separated from the inorganic salt byfiltration, and then the sulfonic acid can be recovered by distillationof the alcoholic solvent. The-sulfonic acids derived from petroleumconstitute an important group of acids which may be used as rawmaterials for the manufacture of regardless of whether derived as theprincipal product of reaction or as the by-product, can be divided intotwo general types, to wit, green acid or acids, and mahogany acid oracids. The green acids are characterized by being water-solubleIllustrating this type of petroleum acid, reference is made to thefollowing patents, to wit:

U. s. Patent No. 1,395,195, dated Jan, 24, 1933,

Limburg; 1,836,429, Dec, 15, 1931, Baddiley et al.; 1,955,859, Apr. 24,1934, Osbum et a1. 1,836,428, Dec. 15,-1931, Baddlley et al.; 1,836,429,Dec. 15, 1931, Baddiley et 9.1.; 1,836,430, Dec. 15, 1931, Baddiley et9.1.; 1,836,431, Dec. 15, 1931, Baddiley et al.; 1,766,063, June24,1930, De Groote et al.; 1,909,295, May 16, 1933, Luther et al.;2,042,410, May 6, 1936, Pierce. Also German Patent No. 550,242, May 19,1932, Chemische Fabrik Pott 8: Co.

Water-soluble salts of true sulfo-naphthenic acids, i. e., chemicalcompounds containing a naphthene nucleus, a sulfonic group, and acarboxy roup, represent a suitable type ofa breakinducing agent. Suchcompounds, of course, must be differentiated from sulfo-naphthenes, i-.e., the

naphthene type of.compounds containing a sulfonic acid group, but nocarboxyl. See British Patent No. 275,267, dated February 4, 1929, toChemische Fabrik Milch, A. G.

As to the manufacture of oil-soluble petroleum sulfonic acids, see thefollowing:

U. S. Patent No. 2,115,843, dated May 3, 1938, Dawson; 2,158,680, May16, 1939, Retailiau; 2,166,117, July 18, 1939, Blumer; 2,168,315, Aug.8, 1939, Blumer; 2,188,770, J an, 30, 1940, Robertson; 2,201,119, May14, 1940, Blumer et al.; 2,203,441, June 4, 1940, Oliver; 2,203,443,June 4, 1940, Ross; 2,203,440, June 4, 1940, Oliver; 2,209,445, July 30,1940, deMering.

The sulfonic acids derived from fatty acids or fatty materials whosewater-soluble salts are con- 1,926,715, Sep. 12, 1933, De Groote t 8.1.,1,988,833,

Jan. 22, 1935, De Groote et a1.

Another type of. a, suitable fatty sulfonic acid is the type which ischaracterized by the fact that an aromatic radical is included and thatthe sulfonic group is directly attached to the aromatic nucleus, insteadof being directly attached to the hydrocarbon chain of the fatty acid.This type is commonly'referred to as a Twitchell reagent.

to Twitchell. 1

See also "Arylstearic Acids from Oleic Aci A. J. Stirton and R. F.Peterson, Industrial and Engineering Chemistry, July 1939, p, p.856-858, and "Sulfonated Arylstearic Acids," A. J, Stirton, R. F. Personand P. H. Groggins, Industrial and Engineering Chemistry, August, 1940,p. p 1136-37. Another class of suitable sulfonic acids which may beemployed as raw materials, include the alkylated aromatic sulfonicacids. Although such acids may be derived from monocyclic aromaticcompounds, such as cymene or the like, it is preferable that they bederived from polycyclic aromatic compounds, such as naphthalene, an-

thracene, diphenyl, etc. Generally speaking, it is usually preferable touse naphthalene for vari- .ous reasons, but particularly due to its lowcost. In regard to the uncondensed'polycyclic compounds, it is generallydesirable to use diphenyl or hydroxyl diphenyl. Although reference hasbeen made to compounds derived from naphthalene, it is obvious thatsimilar compounds, 1. e., alkylated sulfonic acids, can be derived fromany other suitable polycyclic material, condensed or uncondensed, ormay. be derived from a monocyclic material. The production of alkylatednaphthalene sulfonic acids is described in U. S.

Patent No. 2,076,623, dated April 13, 1937, to De Groote et a1.

In some instance compounds of the kind described are manufactured mostexpediently from oleflnes or diolefineaas, for instance, the typeillustrated in U. S. Patent No. 2,072,153, dated March 2, 1937, toBruson et al. In some instances it is particularly desirable tointroduce an alkyl radical having more than 10 carbon atoms, andpossibly as many as 30 carbon atoms.

- Such materials may be manufactured in the man- -nucleus, and moreparticularly, an aromatic nucleus, reference is made to'theaforementioned Guenther U. S, Patent No. 1,901,507. Similarly, monodi-,or triamylated naphthalene, which is an article of commerce, may behydrogenated and subjected to sulfonation. Another commerciallyavailable compound, which is suitable for use is retcne sulfonic acid orits sodium salt.

In the manufacture of compounds of the kind previously described, it isnot necessary to employ alkyl alcohols, but if desired, alicyclicalcohols, suchas cyclohexanol, or an aralkyl alcohol, such as benzylalcohol, may be employed, or the equivalent of cyclohexanol, to wit, acyclic olefine may be employed. Obviously, if an 'aralkyl alcohol isemployed, for instance, benzyl alcohol and benzene or naphthalene, oneobtains in essence a diaryl methane; and it is intended to include instance, condensation of two nuclei by introduction of the methylenebridge or substituted methylene bridge derived from formaldehyde or ace-See also U. S. Patent No. 2,218,472,-

tone or'similar compounds. In this connection reference is made to U.'S. Patent No. 1,336,759, dated April 13, 1920, to Schmidt, and toBritish Patent No. 467,998, dated Demember 28, 1935, to Carpmael.

It is well known that sulfonic acids are readily obtained from tallol,rosin, rosin derivatives, and the like. In many instances, the sameprocedure can be applied as is used in the manufacture of sulfonic acidsfrom fatty acids. As to the nature of tallol, which is now availablecommercially in both the crude and refined types, see Ellis, Chemistryof Synthetic Resins, 1935, volume 1, page 754-755. See also U. S. PatentNo. 1,961,963, dated June 5, 1934, to De Groote et al.; U. S. Patent No.1,913,538, dated June 13, 1933, to De Groote et al.; and U. S. PatentNo. 1,910,680; dated May 23, 1933, to De Groote et 8.1. See especially,U. S. Patent No. 2,220,678, dated November 5, 1940, to Cromwell andMerley.

As to certain sulfonic acids containing amino or amido linkages, see thefollowing U. S. Patents to Guenther at 9.1., to wit, No. 1,932,176,dated October 24, 1933, and Nos. 1,932,180, 1,932,178 and 1,932,177, alldated October 24, 1933.

As to aromatic alkylene ether sulfonates and.

similar types, see the following U. S. Patent No. 2,178,831 and2,178,832, both dated November 7,

1939; to Bruson; U. S. Patent No. 2,178,829, dated November 7, 1939, toBruson et al. and U. S; Patent No. 2,184,935, dated December 26, 1939,to

Bruson et 8.1.

'As to sulfo-dicarboxylic acids which are surface-active, if at leastone carboxylic hydrogen atom 'has been replaced by a hydrophobe grouphaving at least 8 carbon atoms, such as an octyl group or the like, seeU. S. Patent No. 2,028,091, dated January 14, 1936; to Jaeger; and U. S.Patent No. 2,176,423, dated October 17, 1939, to Jaeger, a

As to patents illustrating other suitable high molal sulfonic acids,which may be employed as raw materials, see the following patents:

U. S. Patent Nos. 2,110,848, dated Mar. 8, 1938, to De Groote;1,181,172, Oct. 4, 1932, Daimler et al.; 1,916,776, July 4, 1938,Steindorif et al.; 2,106,242, Jan. 25, 1938, De Groote et al.;2,110,847, Mar. 8, 1938, De Groote.

H 'gh molal alcohols, for instance, naphthyl alcohol, can be treated soas to yield a sulfonic" acid. Such high molal alcohol sulfonic acid maybe employed as a raw material. See U. S. Patent No, 2,000,944, dated May14, 1935, to Schrauth. See also the following: 1

U. S. Patent Nos. 2,061,617, dated Nov. 24, 1936,

salt, such as the sodium salt, and the chlorhydrin, such as ethyleneglycol chlorhydrin. *Still another procedure for the manufacture of suchhydroxylated sulfonic acid esters has been illu..- trated in some of thepatents previouslyreferred to, and particularly, the aforementioned DeGroote et a1. U. S. Patent No. 2,106,242, dated January 25, 1938. Seelast three formulas on page 3 of said De Groote et a1. patent.

. In connection with materials ,of the kind typified by these formulas,it is desirable to employ a substituted methyl chloride. For instance,one can obtain diamylated naphthalene, triamylated naphthalene,mono-octylated naphthalene, or the like. Such materials can be convertedinto the substituted naphthyl methylchlorldc by procedure indicated inU. S. Patent No. 2,166,554,

I .dated July 18, 1939,-t0 ROblin.

The preferred way of preparing such materials is to use the proceduredescribed in U. S. Patent No. 2,208,581, dated July 23, 1940, toHoefielmann. Briefly stated, the procedure employed is to ob tain thefree sulfonic acid in an anhydrous state and treat with a compoundcontaining an olefine oxide radical. As typical examples of applicablecompounds, may be mentioned glycerine epichlorihydrin, glycide alcohol,ethylene oxide,

propylene oxide, butene-2-oxide, butene-l-oxide,

isobutylene oxide, butadiene oxide, butadiene dioxide, chloro-preneoxide, isoprene oxide, decencoxide, styrene oxide, cyclohexylene oxide,cyclopentene oxide, etc.

to Downing et, al.; 2,061,618, Nov. 24, 1936, to T Downing et al.;2,061,619, Nov. 24, 1936, to Downing et al.; 2,061,620, Nov. 24, 1936,to Downing et al.; 2,171,117, Aug. 29, 1939, Schrauth et al.; 2,187,338,Jan. 16, 1940, Werntz; 2,187,339, Jan. 16, 1940, Werntz; 1,917,255, July11, 1933, Harris; 2,170,380, Aug. 22, 1939, Holsten; 1,966,177, July 10,1934, Schirm.

The method of manufacturing hydroxylated esters of sulfonic acids iswell known, although direct reaction between the sulfonic acid and apolyhydric alcohol, such as ethylene glycol, is not applicable, for thereason that one obtains little or no yield of the hydroxylated ester.One procedure contemplates the conversion of sul'- fonic acid into thesulfonchloride, and subsequently reacting the sulfonchloride with apolyhydric alcohol, with the liberation of hydrochloric acid. Anotherprocedure involves reaction between the sulfonic acid, or preferably, a

sulfonic acids are insoluble in absence" of a recurring ether linkage.In order to obtain com pounds of the kind herein contemplated, one muststop treatment with the olefine oxide, i. e., oxyalkylation before watersolubility i obtained; and furthermore, it is desirable to stop watersolubility at the earliest stage. In other words, the olefine oxideemployed, whether ethylene oxide, propylene oxide, butylene oxide,glycidol, methyl glycidol, or the like, is a comparatively expensivereagent; and one is only concerned with obtaining a reactive hydroxylradical for a subsequent esterification step. There is no objection tothe presence of a recurring ether linkage, provided that the ester isstill water-insoluble. This 1 may be illustrated in the followingmanner, using ethylene oxide as the reactant:

But materials illustrated by any of the three subsequent types:

Robertson Patent No. 2,188,770. so obtained, contains considerablemoisture and are Just as satisfactory, provided that the ester, prior toesteriflcation with an intermediate product of the kind subsequentlydescribed in detail, is water-insoluble. In some instances,- thepresence of the recurring ether linkage may give some added desirablecharacteristic. Ordinarily speaking, one is concerned only with minimumreactant cost; and thus, the use of an excess amount of the olefineoxide is not justified. One is not attempting to obtain water solubilityby means of the expensive oxyalkylation step. As has been emphasized,the ester obtained \must be water-insoluble, regardless of how much orhow little alkylene oxide is employed. Generally speaking, 40 moles ofalkylene oxide per mole of sulfonic acid may be considered as an upperlimit, but obviously, solubility is influenced by the alkylene oxideemployed. Butylene oxide naturally will not cause a sulfonic acid to beconverted into a water-soluble ester as readily as ethylene oxide.

It is to be particularly noted that the procedure herein contemplated isespecially valuable, in

producing desirable materials from comparative- Hydrorylated sulfonicacid esters, Example 1 A mahogany sulfonate obtained from themanufacture of white oil from Pennsylvania grade of crude petroleum istreated'in the manner described in the aforementioned Kessler andSalzmann Patent No. 2,125,300. The material so obtained may containmoisture in varying amounts from a few tenths of a percent, to anappreciable amount. If the amount of moisture present represent morethan two or three percent, or even in such instances where thisrelatively small percentage is present, it is preferably converted tothe anhydrous state by admixture with xylene; or a similar high boilingsolvent. The amount of solvent employed may be several times the volumeof sulfonate. Such xylene is distilled off and carries with it anymoisture or water present. The vapors are condensed and the waterseparated from the xylene. The xylene can be returned to the sulfonatedmass being hydrated so as to permit a. continumust be dehydrated by anyconventional procedure, such as a vacuum drier, or by means of xylene,or a sim lar high boiling solvent. The

amount-of solvent employed may be several times the volume of sulfonate.Such xylene is distilled off and carries with it any moistureor waterpresent. The vapors are condensed and the Waous proces in which thexylene is used repeatedly. When the sulfonation mass is reduced to asubstantially anhydrous state, the xylene is distilled off, unless'it isdesired that a small amount be present, so as to yield a fluidsulfonated mass forsubsequent reaction. The anhydrous sulfonic acid. soobtained,'in the presence or absence of a selected inert solvent. isreacted with one to three moles of ethylene oxide in the mannerdescribed in the aforementioned Hoeffelmann Patent No. 2208,581, so asto yield a water-insoluble ester.

Hydrorylated sulfonz'c acid esters, Example 2 Green acids are obtainedfrom a Gulf Coast lubricating oil distillate having an S. U. viscosityat 100 F. of about 400 seconds. The procedure employed is that describedin the aforementioned The material,

ter separated from the xylene. The xylene can be returned to thesulfonated mass being hydrated so as to permit a continuous process inwhich, the xylene is used repeatedly. When the sulfonation mass isreduced to a substantially anhydrous state, the xylene is distilled off,unless it is desired that a small amount be present, so as to yield afluid sulfonated mass for subsequent reaction, The anhydrous: sulfonicacid, so obtained, in the presence or absence of a selected inertsolvent, is reacted with one to three moles of ethylene oxide in themanner described in the aforementioned Hoeifelmann Patent No. 2,208,581,so as to yield a water-insoluble ester.

Hydroxylated suljonic acid esters, Example 3 Dipropyl naphthalenemono-sulfonic acid is obtained in the anhydrous state by passing drycarbon dioxide gas through the same at a temperature suflicient toinsure its fluidity. The dried material is admixed with about 50% byweight of xylene and is treated with one to three moles of ethyleneoxide in the manner described in the aforementioned Hoeffelmann PatentNo. 2,208,581, so as to yield a water-insoluble ester. The xylene canthen be removed by distillation. Esterification can be conducted in theabsence of xylene, if desired.

Hydromylated sulfonic acid esters, Exa-mple4 The sulfonic acidderivative of stearic acid is produced according to Example 1, ofaforementioned Gunther and Hetzer Patent No. 1,926,442. The sulfostearicacid, so obtained, is converted into the anhydrous state by any suitableprocedure. It may be heated .to approximately to C., and dried carbondioxide gas passed through until the material is anhydrous, It may 'bedried in a vacuum drier, so as to yield an anhydrous material. It may bedistilled in the presence of an insoluble solvent such as xylene, sothat the xylene is permitted to carry off water during the distillation.Vapors, so obtained, are condensed and the water separated from thexylene. The xylene can be returned for re-circulation so as to carry onmore water.

Having obtained an anhydrous material of the kind above described, it isdilutedwith several time's its weight of anhydrous ethyl alcohol andrefluxed until the carboxyl hydrogen atom has been replaced by an ethyl,radical. One pound mole of the anhydrous ethyl stearate sulfonic acid,so obtained, is treated with one to three moles of ethylene oxide in themanner described in the aforementioned Hoefielmann Patent No. 2,208,581,so as to yield a water-insoluble ester.

Hydromylated sulfonic acid esters, Example 5 decomposition of suchorganic acid sulfates,

separation is permittedand thewaste acid withdrawn. The mass, soobtained, is neutralized to the methyl orange indicator end-point. so asto neutralize all sulfonic acid radicals present. The materials then isdissolved in several times its volume of water and extracted with asuitable solvent, such as petroleum ether, benzol, or the like, so as toremove unsulfated fatty material. The dilute solution of thesulfo-aromatic material, so obtained, is converted into the anhydrousstate by any suitable procedure. It may be heated to approximately 110to 120 C., and dried carbon dioxide gas passed through until thematerial is anhydrous. It may be dried in a vacuum drier, so as to yieldan anhydrous material. It

may be distilled in the presence of an insoluble solvent, such asxylene, so that the xylene is permitted to carry off water duringdistillation. Vapors, so obtained, are condensed and the water separatedfrom the xylene. The xylene can be returned for re-circulation to carryoil more water. In any event the anhydrous material having atom by anethyl group. One pound mole of the anhydrous sulfo-phenol stearic acidethyl ester is treated with one to three moles of ethylene oxide in themanner described in the aforementioned Hoefielmann Patent No. 2,208,581,so as to yield a water-insoluble ester.

Hydroxylated sulfonic acid esters, Example 6 Tallol is converted intothe hydroxy ethyl ester in the manner described in Example 4 of theaforementioned British Patent No. 340,272. The hydroxy ethyl ester isthen esterified in equal molal proportions with chloroacetic acid. Theproduct, so obtained, is treated in the conventional manner with onemole of sodium sulfite with the elimination of sodium chloride. Thesodium sulfonate, so obtained, is dissolved in alcohol and the freesulfonic acid liberated in the manner previously suggested. The sulfonicacid, so obtained, is anhydrous or can be converted into the anhydrousstate by any suitable procedure.

It may be heated to approximately 110 to 120 C.

and dried carbon dioxide gas passed through until the material isanhydrous. It may be dried in a vacuum drier, so as to yield ananhydrous material. It may be distilled in the presence of an insolublesolid, such as xylene, so that the xylene is permitted to carry on waterduring the distillation. Vapors, so obtained, are condensed and thewater separated from the xylene. The xylene can be returned forre-circulation, so as to carry off more water.

Having obtained an. anhydrous material of the kind above described, itis diluted ,with several times its weight of anhydrous ethyl alcohol andrefluxed until the carboxyl hydrogen atom has been replaced by an ethylradical. Qne pound mole of the anhydrous ethyl ester sulfonic acid,

so obt'ained, is treated with one to three moles of 2,aoa,o4c

Hpdroxylated sulfonic acid esters, Example 7 Dipentene is converted intothe water-soluble sulfonic acid following the specific directions 01 theaforementioned Cromwell and Merley Patent No. 2,220,678. The sulfonic,acid is dehydrated and treated with ethylene oxide in the same manner asin Example 6, preceding, so as to yield a water-insoluble ester.

Hydroxylated sullondc acid esters, Example 8 A crude distilled pine oilis sulfonated in the manner described in Example 5 of the aforementionedCromwell and Merley patent. The sulfonic acid is dehydrated and treatedwith ethylene oxide in the same manner as in Example 6, preceding, so asto yield a water-insoluble ester.

Hydroxylated suljonic acid esters, Example 9 Commercial abietic acid orcrude resin is-su'lfonated in the manner described in Example 6 of theaforementioned Cromwell and Merley patent. The sulfonic acid isdehydrated and treated with ethylene oxide in the same manner as inExample 6, preceding, so as to yield a waterinsoluble ester.

Hydroxylated sulfomc acid esters, Example 10 The same procedure isfollowed as in the preceding Examples 1 to 9, inclusive, except thatfour to six moles of ethylene oxide are employed instead of one to threemoles.

Hydroxylated sulfoniz; acid esters, Example 11 The sam procedure isfollowed as in Examples 1 to 10, inclusive, except that propylene oxideor butylene oxide is substituted for ethylene oxide.

Thus, having obtained hydroxylated waterinsoluble esters (and they maybe polyhydroxylated and may or may not contain the recurring etherlinkage), the next step is to react them with a dibasic ester of thekind previously described. Such reaction, of course, is merely anesterification reaction.

Intermediate product, Example I A one pound mole of nonaethylene glycolis re; acted with two pound moles of maleic anhydrlde so as to formnonaethylene glycol dihydrogen dimaleate.

Intermediate product, Example 2 A mixture of lower non-distillablepolyethylene glycols, representing approximately decatotetra-decaethylene glycol, is substituted for nonaethylene glycol in thepreceding example.

Irutermediate product, Example 3 paratively longer period of reactiontime. Also,

it is desirable to add a small fraction of asuitable catalyst, say,one-fourth of 1% of toluene sulfonic acid, and pass a dried inert gasthrough the reaction mass.

Intermediate product, Example 4 Adipic acid is substituted for maleicanhydrid in Examples 1-3, preceding.

Intermediate product, Example Oxalic acid issubstituted for maleicanhydride in Examples 1-3, preceding.

Intermediate iproduct, Example 6 Citric acid substituted for maleicanhydride in, Examples 1-3, preceding.

Intermediate product, Example 7 Succlnic anhydride is substituted formaleic anhydride in Examples 1-3, preceding.

Compositions of matter, Example 1 A pound mole of an intermediateproduct of the kind described in Intermediate product, Examples 1, 2 and3, above, is reacted with 2 pound moles of a material of the kinddescribed under "Hydroxylated sulfonic acid ester, Example 1, preceding,until substantially all dibasic carboxyl acidity has disappeared. Timeof reaction may,

A material of the kind illustrated by Hydroxylated sulfonic acid ester,Example 3 is substituted for ,lHydroxylated sulfonic acid ester, Example1, in Composition of matter, Example 1, preceding. 1

Composition of matter, Example 4 A material of the kind illustrated byHy-Q droxylated sulfonic acid ester, Example 4 is substituted forHydroxylated sulfonic acid ester, Example 1," in Composition of matter,Example 1, preceding.

Composition of matter; Example 5 A material of the kind illustrated byHy! droxylated sulfonic acid ester, Example 5 is substituted forHydroxylated sulfonic acid ester. Example 1, in Composition of matter,Example 1, preceding.

Composition of matter, Example 6 A material of the kind illustrated byHydroxylated sulfonic acid ester, Example 6 is substituted for"Hydroxylated sulfonic acid ester, Example 1, in Composition'of matter,Example 1, preceding.

Composition of matter, Example A material of the kind illustrated byfHydroxylated sulfonic acid ester, Example 7 is substituted forHydroxylated sulfonic acid ester, Example 1, in Composition of matter,Example 1, preceding.

Composition of matter, Example 8 i A material of the kind illustrated byHystituted for Hydroxylated sulfonic acid ester, Example 1, inComposition of matter, Example 1, preceding,

- Composition of matter, Example 9 In Composition of matter, Examples1-8, preceding, any residual aciditypresent is removed by cautiouslyadding a dilute solution of ammonium hydroxide until the resultantproduct larly in dilute form.

giveaa clear,'-"limpid solution in water, particu- Composition ofmatter, Example 10 In Composition of matter, Examples 1-8, preceding,any residual acidity present is removed by cautiously adding a dilutesolution of triethanolamine until the resultant product gives a clear,limpid solution in water, particularly in dilute form. 1

Composition of matter, Example 11 In Composition of matter, Examples1-8, preceding, any residual acidity present is removed by cautiouslyadding a dilute solution of tri-(hydroxymethyDaminomethane until theresultant product gives a clear, limpid solution in water, particularlyin dilute form.

Composition of matter, Example 12 The same procedure is followed as inComposition of matter, Examples 111, inclusive, except that anintermediate product of the kind exemplifled by Intermediate product,Example 4, is substituted for that in Intermediate product, Ex amples 1,2 and 3.

Composition of matter, Example 13 The same procedure is followed as inComposition of matter, Examples 1-11, inclusive, exceptthat anintermediate product of the kind exemplified by Intermediate product,Example 5, is

substituted for that in Intermediate product, Examples 1, 2 and 3.

Composition of matter, Example: 14

Composition of matter, Example 15 The same procedure is followed as inComposition of matter, Examples 1-11, inclusive, except that. anintermediate product of the kind exemplifled by Intermediate product;Example 7, is

substituted for that in Intermediate product, Ex-

amples 1, 2 and 3.

It is to be noted that this second step is an esterification reaction,and the same procedure is droxylated sulfonic acid ester, Example 8 issub- 4 employed as suggested above in the preparation of theintermediate product. Needless to say, any particular method may be usedto produce the desired compounds of the kind indicated. In someinstances it may be desirable to conduct the esterification reaction inthe presence of a nonvolatile inert solvent. which simply acts as adiluent or viscosity reducer. V

, In the preceding examples, attention has been directed primarily tothe monomeric form, or at least to the form in which the bifunctionalalcohol, i. e., a. glycol, and the polyfunctional acid, usually abifunctional compound, react to give a chain type compound in which theadjacent acid and glycol nucleus occur as a structuralunit. For

instance, in the monomeric form this may be indicated in the followingmanner:

acid glycol acid If, however, one prepared an intermediate,

' product employing the ratio of three moles of manner I acid glycolacid glycol acid Similarly, three moles of the glycol and four moles ofthe acid would give a combination which may be indicated thus:

acid glycol acid glycol acid glycol acid Another way of stating thematter is that the composition may be indicated in the following manner:

in water, and usually in the presence of soluble calcium or magnesiumsalts, and frequently, in

the presence of significant amounts of either acids or alkalies.

Water solubility can be enhanced in a number 2,868,046 not which mightbe indicated in the followin stone and brick; as a wetting agent andspreader in the application of asphalt in road building and the like. asa constituent of soldering flux preparations; as a flotation reagent inth flotation separation of various minerals; for flocculation andcoagulation of various aqueous suspensions containing negatively chargedparticles,

such as sewage, coal washing waste water, and

various trade wastes and the like; as germicides, insecticides,emulsifiers for cosmetics, spray oils,

water-repellent textile finish, etc. These uses are by no meansexhaustive.

However, the most important phase of the present invention, as far asindustrial application goes, is concerned with the use of the materialspreviously described as demulsiflers for water-inoil emulsions, and morespecifically, emulsions of water or brine in crude petroleum.

We have found that the particular chemical compounds or reagents hereindescribed and desirable for use as demulsifiers, may also be used forother purposes, for instance, as abreak inducer in doctor treatment ofthe kind intended to sweeten gasoline. See U. S. Patent No. 2,157,223,dated May 9, 1939, to Sutton.

Chemical compounds 'of the kind herein described are also of value assurface tension deof ways which have been suggested by previousmolecular weight, for instance, maleic acid, in-

stead of adipic acid;

((1) By using an alcoholic material of lower molecular weight instead ofone of higher molecular weight. v i

In any event, it is to be noted that the compounds of the type hereincontemplated are limited to the water-soluble type, i. e., those whichare self-emulsifying in water, or produce a sol or a molecular solution.

Actually, a reaction involving an alcohol and an ,acid (esterification)may permit small amounts of either one or both of the reactants,depending upon the predetermined proportion, to remain in an unreactedstate. In the actual preparation of compositions of the kind hereincontemplated, any residual acidity can be removed by any suitabl base,for instance, ammonia, triethanolamine, or the like, especially indilute solution. Naturally, precaution should be taken so thatneutralization takes place Without saponification or decomposition ofthe ester. In some cases there is no objection to the presence of theacidic group. Indeed, if a tribasic acid be employed in such a manner asto leave one free carboxyl group, then it is .usually desirable toneutralize such group by means of a suitwashing of fruit, in the acidwashing of building pressants in the acidization of calcareousoilbearing strata by means of strong mineral acid, such as hydrochloricacid. Similarly, some members are effective as surface tensiondepressants or wetting agents in the flooding of exhausted oil-bearingstrata.

As to using compounds of the kind herein de- I scribed as floodingagents for recovering oil from subterranean strata, reference is made tothe procedure described in detail in U. S. Patent No.

. 2,226,119, dated December 24, 1940, to De Groote and Keiser. As tousing compounds of the kind herein described as demulslfiers, or inparticular as surface tension depressants in combination with mineralacid or acidization of oil-bearing strata, reference is made to U. S.Patent No. 2,233,383, dated February 25, 1941,-to De Groote and Keiser.

It will be apparentto those skilled in the art that residual carboxylacidity can be eliminated by esterification with a low molal alcohol,for instance, ethyl, methyl, or propyl alcohol, by conventionalprocedure, so as to give a substantially neutral product. Theintroduction of such low molal hydrophobe groups does not seriouslyaffect the solubility, and in some instances, gives increasedresistance, to soluble calcium and magnesium salts, for such property isof particular value. Usually, however, neutralization with a dilutesolution of ammonia or the like is just as practicable and less expense.

In the hereto appended claims, the word acy is used in reference to theradical RSOz; i. e., one can conveniently consider the sulfonic acidRSOsH in terms of a formula indicating part of its structure, to wit,R.SO2.0H.

In the hereto appended claims the words "polyhydric alcohol" are used intheconventional sens to include not only materials of the typeexemplified by glycerol and ethylene glycol, but also materials of thekind in which the carbon atom chain is interrupted at least once by anoxygen atom, as, for example, diethylene glycol, diglycerol, etc.

It may be well to emphasize that compounds of the kind hereincontemplated may be manufactured by any suitable method; and it is notintended to limit the compounds to any particular' method ofmanufacture. When manufactured by theme of an alkylene oxide. it is ourpreference to use ethylene oxide, propylene oxide, or butylene oxide.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. A water-soluble esteriflcation product, derived by reaction between:(A) two moles of a polyhydric alcohol in which one hydroxy hydrogen atomhas been replaced by the acyl radical 01 a surface-active sultonic acidhaving a molecular weight between 200 and 1,000 and said ester beingwater-insoluble; and (B) at least one mole of a polybasic compound; saidpolybasic compound being the esteriilcation product of (a) apolyalkylene glycol having at least 7 and not more than 17 etherlinkages, and the alkylene radical thereof containing at least 2 and notmore than 6 carbon atoms; and (b) a polybasic carboxy acid having. notmore than 6 carbon atoms; and the ratio of the esteriiying reactantsbeing within the range of more than 1 and not over 2 moles of thepolybasic acid for each mole of the glycol.

2. A water-soluble esteriflcation product, derived by reaction between:(A) two moles of a polylrvdric alcohol in which one hydroxy hydrogenatom has been replaced by the acyl radical of a surface-active sulionicacid having a molecular weight between 200 and 500 and said ester beingwater-insoluble; and (B) at least one mole oi. a polybasic compound;said polybasic compound being the esteriflcation product of (a) apolyalkylene glycol having at least '7 and not more than 17 etherlinkages, and the alkylene radical thereof containing at least 2 and notmore than 6 carbon atoms; and the ratio of the esterii'yingv reactantsbeing within the range of more than 1 and not-over 2 moles of thepolybasic acid for each mole of the glycol.

3. A neutral water-soluble esteriflcation product, derived by reactionbetween:- (A) two moles of a polyhydric alcohol in which one hydroxyhydrogen atom has been replaced by the acyl radi cal of a surface-activesulionic acid having a molecular weight between 200 and 500 andsaidester being water-insoluble; and (B) at least one mole oi a polybasiccompound; said polybasic compound being the esteriflcation product (a) apolyalkylene glycol having at least '1 and not more than 17 etherlinkages, and the alkylene radical thereof containing at least 2 and notmore than 6 carbon atoms; and (b) a polybasic car- 9 andthe ratio of theesterifying reactants being within the range 01 more than 1 and not over2 moles oi the polybasic acid for each mole or the glycol. 5 4. Aneutral water-soluble esteriflcation product, derived by reactionbetween: (A) two moles of a polyhydric alcohol in which one hydroxyhydrogen atom has been replaced by the acyl radical oi! a surface-activesulfonic acid having a molecular weight between 200 and 500 and saidester being water-insoluble; and (B) at least one mole of a dibasiccompound; said dibasic compound being the esteriflcamn product of (a) apolyalkylene glycol having at least 7 and not more than 1"!v etherlinkages, and the alkylene radical thereof containing at least 2'and notmore than 6 carbon atoms; and (b) a dibasic carboxy acid having not morethan 6 carbon atoms: and the ratio of the esterifying reactants beingwithin the range 01' more than 1 and not over 2 moles of the polybasicacid for each mole oi the glycol.

5. A neutral water-soluble esterification product, derived by reactionbetween: (A) two moles hydrogen atom has been replacedby the acylradical of a surface-active sulionic acid having a molecular weightbetween 200 and 500, and said ester being water-insoluble; and (B) atleast one mole of a dibasic compound; said dibasic compound being theesterification product of (a) a polyethylene glycol having at least '7and not morethan 1'7 ether linkages; and (b) a dibasic carboxy acidhaving not more than '6 carbon atoms; and the ratio of the esterifyingreactants being within the range of more than 1 and not over 2 moles ofthe polybasic acid for each mole of the glycol.

6. A neutral water-soluble esteriflcation product, derived by reactionbetween one mole of a dibasic compound and two moles of a polyhydricalcohol in which one hydroxy hydrogen atcm has been replaced by the acylradical of a surface-active cyclic sulfonic acid having a molecularweight between 200 and 500, and said ester being waterinsoluble; thedibasic compound being the esteriiication product of (A) a polyethyleneglycol having at least 7 and not more than 1'7 etherfv linkages and (B)a dibasic carboxy acid having not more than 6 carbon atoms; and theratio of the ate'rifying reactants being within the range of more thanone and not over two moles of the dibasic acid for each mole of theglycol. MELVDI DE GROOTE.

BERNHARD KEIBER.

of a poly dric alcohol in which one hydroxy

